Ruthenium-promoted fluorided alumina as a support for SBF{HD 5{B -HF in paraffin isomerization

ABSTRACT

Paraffin hydrocarbons containing four to eight carbon atoms are isomerized employing SbF5-HF supported on a ruthenium-promoted fluorided alumina.

Unlted States Patent 1 1 1111 3,864,425 Gardner Feb. 4, 1975 RUTHENlUM-PROMOTED FLUORIDED [56] References Cited ALUMINA AS A SUPPORT FOR SBF -HF IN UNITED STATES PATENTS PARAFFIN ISOMERIZATION 3,268,439 8/1966 Tupman et al 260/683.65 Inventor; E Gardner, Bartlesvflle 3,394,202 7/1968 Oelderik 260/683.68 Okla. 3,553,281 1/1971 Goble et al. 260/683.68 3,617,516 11/1971 Gooswilligen et al. 260/683.68 [73] Ass1gnee: Philllps Petroleum Company, 3,646,152 2/1972 Saggitt et al. 260/683.68

Bartlesville, Okla. [22] Filed: Sept. 17, 1973 Primary Examiner-C. Davis [21] Appl. N0.: 398,086 [57] ABSTRACT Paraffin hydrocarbons containing four to eight carbon [52] U.S. Cl. 260/683.68 atoms are isomerized employing w -1 Supported CL t on a ruthenium promoted fluorided alumina [58] Field of Search 260/683.65, 683.68

10 Claims, 2 Drawing Figures FATENTEI] FEB M975 CONVERSiON OF N-HEPTANE, /o N O O l l I CONVERSION OF 2-METHYLHEXANE, /o

TIME ON STREAM, HOURS FIG. I-

TIME ON STREAM, HOURS FIG. 2

RUTHENlUM-PROMOTED FLUORIDED AL-UMINA AS A SUPPORT FOR SBF.-.-HF 1N PARAFFIN ISOMERIZATION This invention relates to the use of SbF,-,-HF. that is.

EXAMPLE 1 A sample of commercial 0.5 wt. percent ruthenium on alumina (VB X 411M311 pills) was l'luorided in a Monel to Ihfi use of HSbF in the 515619191 15911191121109" of P 5 reactor by heating to 300F for2-4 hours in a heliumaffins- I diluted stream of hydrogen fluoride. This was followed in one of more Specific 1151x3915 this invention by heating the reactor contents at 800F for 2-4 hours. laies to the use of ruthemum'Pmmoted fluorideii respectively, in helium and hydrogen. After the hydro- 9 for HSbFfi Paraffin gen purge. the ruthenium-promoted Fluorided alumina TTf P HSbF d H I d I was cooled to room temperature and stored in a bottle. for 2:32: z zi gz s gl ifsgm zi s g ufi A 22.31 g sample of the ruthenium-promoted fluosures as that of us. Pat. No. 3,394,202 the disclosure was placed F T of which is included herein y reference. reactor contents showed a weight gain of 4.78 g atter In accordance with the present invention, the isomcrl $155353? 1532; gg fg t +i iii gf ggg ization of C. -C,. paraffins to more highly branched iso- 1 I I mers is advantageously practiced in the presence of F'? z s s gig i i g SbF,-,HF supported on ruthenium-promoted fluorided Ont 6mm Welg to csupporc compo alumina. Data are included to show that t'luorided alumina treated with rhodium or palladium failed to show 311 A w "1 any advantage Over fluorided alumina as Supports for methylhexane isomerization run were carried opt 11101- SbFTHF The SbFyHF cauuyst on ruthenium vidually over the above supported catalyst at 23 -24 C, promoted fluorided alumina 'gave higher conversion atmosphere. is mols H2/m0l (or and greater selectivity to multibranched products. methylhexane) and a gaseous Space Velocity of 200 The operability of the present invention employing 25 V/V/Hr' ruthenium-promoted fluorided alumina is demon- One feedstock contained 84 mol percent n-heptane strated by Example 1 (n-heptane isomerization and 2- and 16 mol percentmethylcyclohexane; the other feedmethylhexane isomerization). Examples 11. and 111 destock contained 84 mol percent 2-mcthylhexane and scribe the results obtained, respectively, with the palla- 16 mol percent methylcyclohexane. Chromatographic dium and rhodium-treated fluorided aluminas using n analysis of vapor samples at various time intervals demheptane and Z-methylhexane feedstocks. Example 1V is onstrated that normal heptane and 2-methy1hexane a comparative run using fluorided alumina as a support were isomerized to more highly branched C isomers. for SbF -HF in normal heptane and Z-methylhexane The results are shown in Table 1 for the normal heptane isomerizations. run and in Table 11 for the Z-methylhexane run.

TABLE 1 n-Hept tine lsomerization over Shh-HF Composition (Reactor Effluent)" Time on 71 C & 2.2-DMP 2,2.3- 3,3-DMP 2.3-DMP 3-EP Sample Stream Conversion C i-C i-Cs S & TMB & 2-MH & 3-MH & DMCP n-C,

N0. Hrs.) n C 2.4-DMP "Excluding methylcyclohcxanc; 2,2-DMP; 2,4-DMP; 2.2.3-TMB; 3,3-DMP; Z-MH; 2.3-DMP; 3-MH; 3-EF; and DMCP. represent. respectively. 2.2 dimeth lpentane; 2.4-dimcthylpcntanc; 2.2.3-lrimcthy1butanc; 3,3-dimethy1pentune; Z-mcthylhexane; 2.3-dimethy1pentune: S-methylhcxane; 3-ethy1pcntanc. and dimethylcyclopentunc.

TABLE 11 Z-Methylhexane lsomerization over SbF -HF Supported on Ruthenium Promoted Fluorided Alumina 7c Composition (Reactor Effluent) Time on 92 2.2-DMP 2.2,3- 3,3-DMP 2,3-DMP 3-EP Sample Stream Conversion No. i-C i-Ct C.,'s & 2.4-DMP TMB & Z-MH & 3-MH & DMCP n-C,

No. tHrs.) 2-MH No. Based on t3.3-1)MP & 2MH) values See footnote :1 oli'l'ahle l 3 4 EXAMPLE 11 with a helium-diluted stream of hydrogen fluoride at 800F followed by heating at 800F in a helium purge. An 1 1.35 g sample of the above rhodium-fluorided alumina was placed in a nickel tube reactor. The reac- 5 tor contents showed a weight gain of 1.24 g after the sequential treatment of helium-diluted SbF5 and helium-diluted hydrogen fluoride. The catalyst composite contained 9.8 weight percent total of SbF,-, and HF based on the total weight of the supported composition. 1 lsomerization of Z-methylhexane was carried out on h total i h of h Supported composition l diover the above catalyst and the results are shown in vidual isomerizations of nheptane and Z-methylhexane Table. The feedstock W115 115 in Example were carried out over the above supported catalyst at After the 2-methylhexane run. the catalyst was 23-24C, 1.0 atmosphere, 15 mols H /mol n-C (or 2- treated with SbFr, and HF to give a catalyst composite methylhexane) and a gaseous space velocity of 200 15 containing 18.1 weight percent total of SbF.-, and HF V/V/Hr. Feedstocks were as in Example 1. The normal based on the total weight of the supported composition. heptane results are given in Table 111. Results for 2- lsomerization of n-heptane was carried out over the methylhexane are given in Table IV. above catalyst and the results are shown in Table V1.

A sample of commercial 0.5 wt. percent palladium on alumina (/e X Va inch pills) was fluorided as described in Example 1.

A 23.56 g sample of the palladium-fluorided alumina was placed in a nickel tube reactor. The reactor contents showed a weight gain of 6.30 g after the sequential treatment of helium-diluted SbF.-, and heliumdiluted hydrogen fluoride. The catalyst composite contained 21.1 weight percent total of SbF and HF based TABLE 111 n-Heptane lsomerization Over SbF 'HF on Palladium-Fluorided Alumina Support 7: Composition (Reactor Effluent)" Time on 7: Conversion 2,2-DMP 2.2,3- 3.3-DMP 2,3-DMP 3-EP Sample Stream n-C i-C i-C,-; C(s & 2,4-DMP TMB & 2-MH & 3-MH & DMCP n-C,

No. (Hrs.l

"See (malnoua 'l'uhlc I TABLE 1V Z-Methylhexane lsomerization over SbFyHF on Palladium-Fluorided Alumina Support Composition (Reactor Effluent)" Time on '7: 2,2-DMP 2,2,3- 3,3-DMP 2,3-DMP 3-EP Sample Stream Conversion No. i-C i-C, C s 84 2,4-DMP TMB & 2-MH & 3-MH & DMCP n-C No. (Hrs.) 2-MH l 0.5 65.8 0.6 0.2 0.1 14.1 0.6 34.2 19.4 0.4 30.2 2 l 4 53.5 0.7 0.2 0.1 16.6 0.6 46.5 27.8 0.7 6.8 3 3 1 49.2 0.8 0.4 0.1 15.1 0.7 50.8 g 27.7 0.8 3.6 4 4 3 47.6 0.7 0.2 0.1 13.7 0.5 52.4 28.0 0.9 3.5

No. Based on 100 (3,3-DMP 84 2-MH) values "See footnote a Table 1 EXAMPLE 111 The feedstock was as in Example 1.

The isomerizations of Z-methylhexane and wheptane A sample of commercial 0.5 wt. percent rhodium on were carried out at the same conditions described in alumina (M; X /8 inch pills) was fluorided by treatment Examples 1 and 11.

TABLE V Z-Methylhexane lsomerization Over SbFs-HF on Rhodium-Fluorided Alumina Support 7: Composition (Reactor Effluent)" Sample Time on 72 2,2-DMP 2,2,3- 3.3-DMP 2.3-DMP No. Stream Conversion No. i-C; 1-C5 C.,s & 2,4-DMP TMB & 2-MH & 3-MH 3-EP n-C-,

(Hrs.) Z-MH No. Based on 100 (3.3.-DMP & Z-MH) values "See footnote a Table l TABLE VI n-Heptane lsomerization Over SbF,,-HF on Rhodium-Fluorided Alumina Support "/1 Composition (Reactor Effluent)" Time on 7! Conversion 2.2-DMP 2.2,3- 3.3-DMP 2,3-DMP 3-EP Sample Stream n-C i-C Cr, C. & 2,4-DMP TMP & Z-MH 8; 3-MH & DMCP n-C;

No. (Hrs) "Setfootnote a Table 1 EXAMPLE 1V Curve Description Example An 1 1.68 g sample of fluorided alumina was placed A Ruthenium-fluorided alumina l B Fluorided alumina 1V 1n a nlckel tube reactor. The reactor contents showed C puuudiumfluorided alumina H a welght galn of 1.10 g after the sequennal treatment D Rhodium-fluorided alumina lll 0f helium-diluted SbF,-, and helium-diluted hydrogen fluoride. The catalyst composite contained 8.6 wt. percent total of SbFa and HF based on the total weight of the supported composition.

Individual normal heptane and Z-methylhexane isomerization runs were carried out over the above catalyst Curve Descript Example at the same conditions as feedstocks as used in Exam- I I A Ruthemum-lluonded alumlna l ples 1, 11 and Ill. The results of the normal heptane runs B Fluorided alumina IV are shown in Table VII and the results of the 2- C pullflllum'fluullded m H D Rhodlum-l'luorlded alumina lll methylhexane runs are shown 1n Table Vlll.

TABLE Vll n-Heptane lsomerization over SbFs-HF Supported on Fluorided Alumina Composition (Reactor Effluentl" Time on 2,2-DMP 2.2,3- 3.3-DMP 2,3-DMP Sample Stream Conversion C i-C l-Cs Cr 's & TMB & Z-MH & 3-MH 3-EP n-C-,

No. (Hrs) n-C; 2,4-DMP See footnote a Table 1 TABLE Vlll Z-Methylhexane lsomerization over SbFs-HF Supported on Fluorided Alumina /1 Composition (Reactor Effluent) Time on 7: 2,2-DMP 2,2.3- 3.3-DMP 2,3-DMP Sample Stream Conversion No. 1C i-Cs C fs & 2.4-DMP TMB & Z-MH & 3-MH 3-EP n-C No. Hrs. Z-MH The results of the aforementioned runs are shown on the attached drawings in which FIGS. 1 and 11 represent graphically the results of the foregoingrruns'.

Referring now to these figures, FIG. 1 represents the results of u-heptane isomerization runs, as follows:

Summarily, these figures indicate that HSbF supported on ruthenium-promoted fluorided alumina gives the highest conversion ofn-heptane and 2-methy1hexane to more highly branched isomers.

In view of the foregoing actually-performed runs. the

following statements as to the applicability and operability of the invention are made.

The invention is applicable to any paraffin containing 4 to 8 carbon atoms, employing HSbF supported on a ruthenium-promoted fluorided alumina.

The quantity of ruthenium metal deposited on the catalyst can be in the range of from about 0.05 to about 10 weight percent based upon the total weight of the supported composition. Preferably the quantity of ruthenium will be within the range of from about 0.1 to about 2 weight percent on the aforesaid basis.

EXAMPLE v The runs were made at 0C, atmospheric pressure, mols H lmol n-heptane and the feed contained 16 mol percent methylcyclohexane and 84 mol percent Itheptane. The glc results (excluding n-heptane) in Table 1X indicate the greater selectivity to multibranched products in the ruthenium-promoted fluorided alumina 10 system as reflected by the higher values for the "Ratio TABLE 1X n-Heptane isomerization Runs with SbF.-.-HF on Ruthenium Promoted Fluorided Alumina and SbF,-.-HF on Fluorided Alumina "Ruthenium promoted fluorided alumina; 33.1 Weight percent total of SbF and HF based on the total weight of the supported composition.

"Fluorided alumina; 10.3 weight percent total of Shh and HF based on the total weight of the supported composition.

Glc analyses of fraction of product (excluding n-Cflt No. Abbreviations are det'med in footnote to Table l.

The total quantity of SbF.-, and HF, which can be considered as HSbF.,, based on the total weight of the supported composition can be within the range of from about 1 to about 50 weight percent and preferably it will be within the range of from about 5 to about weight percent.

The hydrocarbon feed will be introduced into contact with the catalyst with hydrogen, the molar ratio of hydrogen to hydrocarbon feedstock being within the range of from about 0.1 to about 100 and preferably from about 1 to about 20.

The isomerization can be conducted at a temperature within the range of from about --80" to about 100C. Preferably, it will be conducted at a temperature within the range of from about 0 to about C. The pressure can be within the range of from about 0.1 to about 70 atmospheres. Preferably, the pressure will be within the range of from about 1 to about 5 atmospheres.

The isomerization can be conducted at a gaseous space velocity within the range of from about 5 to about 5,000 volumes of gaseous feed (hydrocarbon plus hydrogen feed) per volume of catalyst per hour and preferably within the range of from about 100 to 1,000 volumes per volume per hour.

The runs described below in Example V were carried out to compare the SbF -,-HF catalyst on. rutheniumpromoted fluorided alumina with the SbF -HF catalyst on fluorided alumina in regard to selectivity to multibranched products obtained in a normal heptane isomerization.

It will be evident in view of the foregoing that various modificationscan be made to the method of this invention. Such, however, are considered as being within the scope of the invention.

What is claimed is:

l. A method of isomerizing paraffin hydrocarbons containing 4 to 8 carbon atoms contained in a feedstream which comprises passing said feedstream and hydrogen into contact with a composition comprising a ruthenium-promoted fluorided alumina catalyst comprising SbF -,-HF to isomerize said hydrocarbons and recovering the isomerized hydrocarbons.

2. The method ofclaim l in which ruthenium is present in an amount within the range of from about 0.05 to about 10 weight percent of said composition.

3. The method of claim 1 in which said SbF -HF is present in an amount within the range of from about 1 to about 50 percent of said composition.

4. The method of claim 1 in which said feedstream is passed into contact with said catalyst at a temperature within the rangeof from about to about C.

5. The method of claim 1 in which said feedstream is passed into contact with said catalyst at a pressure within the range of from about 0.1 to about 70'atmospheres.

6. The method of claim 1 in which said feedstream and said hydrogen are passed into contact with said cat- 9 7. The method of claim 1 in which said paraffin hydrocarbon is chosen from n-heptane and 2- methylhexane, said composition contains about ()5 weight percent ruthenium and about 17.7 weight percent HSbF and said feedstream and hydrogen are contacted with said composition at a gaseous space velocity of about 200, a temperature of about 23C and a pressure of about 1 atmosphere.

8. The method of claim 7 in which said feedstock contains about 84 mol percent a-heptane.

contains about 84 mol percent Z-methylhexane. 

1. A METHOD OF ISOMERIZING PARAFFIN HYDROCARBONS CONTAINING 4 TO 8 CARBON ATOMS CONTAINED IN A FEEDSTREAM WHICH COMPRISES PASSING SAID FEEDSTREAM AND HYDROGEN INTO CONTACT WITH A COMPOSITION COMPRISING RUTHENIUM-PROMTED
 2. The method of claim 1 in which ruthenium is present in an amount within the range of from about 0.05 to about 10 weight percent of said composition.
 3. The method of claim 1 in which said SbF5-HF is present in an amount within the range of from about 1 to about 50 percent of said composition.
 4. The method of claim 1 in which said feedstream is passed into contact with said catalyst at a temperature within the range of from about -80* to about 100*C.
 5. The method of claim 1 in which said feedstream is passed into contact with said catalyst at a pressure within the range of from about 0.1 to about 70 atmospheres.
 6. The method of claim 1 in which said feedstream and said hydrogen are passed into contact with said catalyst at a space velocity within the range of from about 5 to about 5,000 volumes per volume of catalyst per hour.
 7. The method of claim 1 in which said paraffin hydrocarbon is chosen from n-heptane and 2-methylhexane, said composition contains about 0.5 weight percent ruthenium and about 17.7 weight percent HSbF6 and said feedstream and hydrogen are contacted with said composition at a gaseous space velocity of about 200, a temperature of about 23*C and a pressure of about 1 atmosphere.
 8. The method of claim 7 in which said feedstock contains about 84 mol percent n-heptane.
 9. The method of claim 1 in which said paraffin hydrocarbon is 2-methylhexane, said composition contains about 0.5 weight percent ruthenium and about 17.7 weight percent HSbF6 and said feedstream and hydrogen are contacted with said composition at a gaseous space velocity of about 200, a temperature of about 23*C and a pressure of about 1 atmosphere.
 10. The method of claim 7 in which said feedstock contains about 84 mol percent 2-methylhexane. 